Rica R A, Jiménez M L, Delgado A V
Department of Applied Physics, School of Sciences, Campus Fuentenueva University of Granada, 18071 Granada, Spain.
Langmuir. 2009 Sep 15;25(18):10587-94. doi: 10.1021/la9013976.
In this work we consider how the spheroidal shape of colloidal particles and their concentration in suspension influence their electrokinetic properties in alternating (ac) electric fields, in particular, their electrophoretic mobility, traditionally known as dynamic mobility in the case of ac fields. Elaboration of a formula for the mobility is based on two previous models related to the electrokinetic response of spheroids in dilute suspensions, completed by means of an approximate formula to account for the finite concentration of particles. At the end, semianalytical formulas have been obtained in the form of the classical Helmholtz-Smoluchowski equation for the mobility with three frequency-dependent factors, each dealing with inertia relaxation, electric double layer polarization and volume fraction effects. The two resulting expressions differ basically in their consideration of double layer polarization processes, as one considers only Maxwell-Wagner-O'Konski polarization (related to the mismatch between the conductivities of the particles plus their double layers and the liquid medium), and the other also includes the concentration polarization effect. Since in the frequency range typically used in dynamic mobility measurements the latter polarization has already relaxed, both models are capable of accounting for the dynamic mobility data experimentally obtained on elongated goethite particles in the 1-18 MHz frequency range. Results are presented concerning the effects of volume fraction, ionic strength, and pH, and they indicate that the models are good descriptions of the electrokinetics of these systems, and that dynamic mobility is very sensitive not only to the zeta potential of the particles, but also to their concentration, shape, and average size, and to the stability of the suspensions. The effects of ionic strength and pH on the dynamic mobility are very well captured by both models, and a consistent description of the dimensions and zeta potentials of the particles is reached. Increasing the volume fraction of the suspensions produces mobility variations that are only partially described by the theoretical calculations due to the likely flocculation of the particles, mainly associated with the fact that goethite particles are not homogeneously charged, with attraction between positive and negative patches being possible.
在本研究中,我们探讨了胶体颗粒的球形形状及其在悬浮液中的浓度如何影响其在交变(ac)电场中的电动性质,特别是其电泳迁移率,在交流电场的情况下传统上称为动态迁移率。迁移率公式的推导基于之前两个与稀悬浮液中球体的电动响应相关的模型,并通过一个近似公式进行补充,以考虑颗粒的有限浓度。最后,得到了半解析公式,其形式为经典的亥姆霍兹 - 斯莫卢霍夫斯基迁移率方程,包含三个频率相关因子,分别处理惯性弛豫、电双层极化和体积分数效应。所得的两个表达式在对双层极化过程的考虑上基本不同,一个仅考虑麦克斯韦 - 瓦格纳 - 奥康斯基极化(与颗粒及其双层的电导率与液体介质的电导率不匹配有关),另一个还包括浓度极化效应。由于在动态迁移率测量通常使用的频率范围内,后者的极化已经弛豫,因此这两个模型都能够解释在1 - 18 MHz频率范围内对细长针铁矿颗粒实验获得的动态迁移率数据。给出了关于体积分数、离子强度和pH值影响的结果,结果表明这些模型很好地描述了这些系统的电动现象,并且动态迁移率不仅对颗粒的zeta电位非常敏感,而且对其浓度、形状和平均尺寸以及悬浮液的稳定性也很敏感。两个模型都很好地捕捉到了离子强度和pH值对动态迁移率的影响,并且对颗粒的尺寸和zeta电位达成了一致的描述。增加悬浮液的体积分数会产生迁移率变化,由于颗粒可能发生絮凝,理论计算只能部分描述这种变化,这主要与针铁矿颗粒电荷不均匀有关,正负电荷区域之间可能存在吸引力。